JP6422712B2 - Polycarbonate resin composition and molded product - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded article, and more particularly, to a polycarbonate resin composition and a molded article having high thermal conductivity and high electromagnetic shielding properties and excellent in flame retardancy and strength.

  Polycarbonate resin is excellent in impact resistance, heat resistance, electrical insulation, dimensional stability, etc., and has a good balance of these characteristics. Therefore, electrical and electronic equipment parts, precision machine parts, vehicle parts, OA equipment parts. Widely used in such fields.

  However, since the polycarbonate resin has a high electric resistivity and is easily charged, it may cause various troubles due to static electricity. In the above fields, most devices are equipped with components that generate heat. However, in recent years, as the performance of devices increases, the amount of power consumed per component increases and the amount of heat generated from components tends to increase. Therefore, there is a need for a polycarbonate resin material that exhibits higher thermal conductivity.

  As a method of imparting thermal conductivity to a polycarbonate resin material, a method of blending various thermal conductive fillers is known, and Patent Documents 1 to 6 show polycarbonate resin compositions having good thermal conductivity. ing. However, these polycarbonate resin compositions can exhibit good thermal conductivity, but have the disadvantage that the impact resistance is deteriorated, and the thermal conductivity is excellent, and the impact resistance. In addition, an excellent polycarbonate resin composition is desired.

  Furthermore, in recent years, electronic devices such as personal computers, various portable terminals, and digital cameras have been rapidly increasing in circuit integration, density, and high-speed processing due to the reduction in size and weight and performance. When electromagnetic waves enter the electronic device from the outside, there is a problem of causing malfunctions and poor processing. For this reason, the housing | casing etc. of an electronic device have become essential [the function which shields the electromagnetic wave from the outside, and prevents the electromagnetic wave leakage outside].

In order to impart an electromagnetic wave shielding function to a casing or the like of an electronic device, there is a method of conducting electromagnetic coating to shield the electromagnetic wave. However, a complicated coating process is required, and there are drawbacks such as easy peeling of the conductive layer. The method of molding from a resin composition containing a conductive filler is advantageous because it does not require post-processing and there is no risk of peeling, but if the conductivity is insufficient or a large amount is contained, the mechanical properties are significantly reduced. Resulting in.
Patent Document 7 proposes an electromagnetic wave shielding resin composition in which a polycarbonate resin is blended with an ABS resin and / or a polyester resin with a fibrous conductive filler, and polycaprolactone is blended. It is still not enough to solve the problems of shielding properties, high thermal conductivity, flame retardancy and strength.

JP 2007-16093 A JP 2007-238917 A JP 2008-127554 A JP 2008-163270 A JP 2009-161582 A JP 2011-16936 A Japanese Patent Laid-Open No. 06-240128

  An object (issue) of the present invention is to provide a polycarbonate resin composition having high thermal conductivity and high electromagnetic shielding properties, and excellent in flame retardancy and strength.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that polycarbonate resin contains carbon fibers containing nickel-coated carbon fibers, phosphorus-based flame retardants, and fluoropolymers in specific amounts, respectively. The present inventors have found that a resin composition solves the above problems and have completed the present invention.
The present invention provides the following polycarbonate resin composition and molded article.

[1] 5 to 100 parts by mass of carbon fiber (B) containing nickel-coated carbon fiber, 3 to 30 parts by mass of phosphorus-based flame retardant (C) and fluoropolymer (D) with respect to 100 parts by mass of polycarbonate resin (A) ) In an amount of 0.001 to 5 parts by mass.
[2] The polycarbonate resin composition according to the above [1], wherein the carbon fiber (B) containing nickel-coated carbon fiber is a mixture of carbon fiber (B1) and nickel-coated carbon fiber (B2).
[3] The polycarbonate resin composition according to the above [2], wherein the mass ratio (B1 / B2) of the carbon fiber (B1) to the nickel-coated carbon fiber (B2) is 1/9 to 9/1.
[4] The polycarbonate resin composition according to the above [1], wherein the phosphorus flame retardant (C) is a phosphate ester compound or a phosphazene compound.
[5] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [4].

  According to the polycarbonate resin composition of the present invention, it is possible to provide a polycarbonate resin composition having high thermal conductivity and high electromagnetic shielding properties and excellent in flame retardancy and strength.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

[Overview]
The polycarbonate resin composition of the present invention is 5 to 100 parts by mass of carbon fiber (B) containing nickel-coated carbon fiber and 3 to 30 parts by mass of phosphorus flame retardant (C) with respect to 100 parts by mass of polycarbonate resin (A). Part and fluoropolymer (D) are contained 0.001-5 mass parts.

[Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin (A) used in this invention, A polycarbonate resin may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —.
In the formula, X is generally a hydrocarbon, but for imparting various properties, X into which a hetero atom or a hetero bond is introduced may be used.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Further, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

  Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

9,9-bis (4-hydroxyphenyl) fluorene,
Cardio structure-containing bisphenols such as 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

4,4′-dihydroxydiphenyl sulfide,
Dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

4,4′-dihydroxydiphenyl sulfone,
Dihydroxydiaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;
Etc.

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are particularly preferable, and 2,2-bis (4-hydroxyphenyl) propane (especially from the viewpoint of impact resistance and heat resistance). That is, bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

In addition, when an example of a monomer that is a raw material of the aliphatic polycarbonate resin is given,
Ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3- Alkanediols such as diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol;

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

  Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, a particularly preferable one of these methods will be described in detail.

.. Interfacial polymerization method First, the case where a polycarbonate resin is produced by the interfacial polymerization method will be described.
In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where a polycarbonate resin is manufactured by the melt transesterification method is demonstrated.
In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, carbonic acid diester may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin is obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound, and above all, 1.01 mol or more is used. It is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the polycarbonate resin and the like, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, 1 type may be used for a catalyst deactivator and it may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matters regarding the polycarbonate resin (A) The molecular weight of the polycarbonate resin (A) may be appropriately selected and determined. The viscosity average molecular weight [Mv] is usually 10,000 or more, preferably 16000 or more, more preferably 17000 or more. More preferably, it is 18000 or more, and is usually 40000 or less, preferably 30000 or less.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of polycarbonate resin can be improved more. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of a resin composition can be improved more.

  In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resin (A). Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[Carbon fiber containing nickel-coated carbon fiber (B)]
The polycarbonate resin composition of the present invention contains carbon fibers (B) including nickel-coated carbon fibers. The carbon fiber (B) including the nickel-coated carbon fiber is preferably a mixture of the carbon fiber (B1) and the nickel-coated carbon fiber (B2), and both the carbon fiber (B1) and the nickel-coated carbon fiber (B2) are used. It is preferable to contain.

As the carbon fiber (B1), any of pitch-based, PAN-based (polyacrylonitrile-based), rayon-based and the like can be used, but pitch-based carbon fibers are preferable from the viewpoint of impact resistance and thermal conductivity. The average fiber diameter of the carbon fibers (B1) is preferably 20 μm or less, and most preferably in the range of 5 to 8 μm from the balance of fluidity, impact resistance, dimensional stability and appearance. If the average fiber diameter exceeds 20 μm, the balance between dimensional stability and impact resistance is lowered, which is not preferable.
Moreover, it is preferable from the point of balance of impact resistance, dimensional stability, thermal conductivity, and external appearance that the average fiber length in the composition is in the range of 0.1 to 2 mm.

The carbon fiber (B1) is preferably subjected to a surface treatment, and the tensile strength and bending strength as the resin composition are improved. Any commonly used surface treating agent can be used, and examples thereof include epoxy sizing agents, urethane sizing agents, epoxy-urentane sizing agents, polyamide sizing agents, and olefin sizing agents. Among these, epoxy-based, polyamide-based, and urethane-based materials are preferable because of their good dispersibility with respect to the polycarbonate resin.
The amount of the surface treatment agent is preferably in the range of 0.5 to 15 parts by mass and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the carbon fiber (B1).

The nickel-coated carbon fiber (B2) is a carbon fiber coated with nickel or a nickel alloy by a known method such as a plating method or a vapor deposition method. The carbon fiber can be the same as the carbon fiber (B1), and may be any of pitch-based and PAN-based.
The average fiber diameter of the nickel-coated carbon fiber (B2) is preferably 20 μm or less, and most preferably in the range of 5 to 8 μm from the balance of fluidity, impact resistance, dimensional stability and appearance. If the average fiber diameter exceeds 20 μm, the balance between dimensional stability and impact resistance is lowered, which is not preferable.
Moreover, it is preferable from the point of balance of impact resistance, dimensional stability, thermal conductivity, electromagnetic wave shielding property, and an external appearance that the average fiber length in the composition is in the range of 0.1 to 2 mm.

The nickel-coated carbon fiber (B2) is preferably subjected to surface treatment, and the tensile strength and bending strength as the resin composition are improved. Any commonly used surface treating agent can be used, and examples thereof include epoxy sizing agents, urethane sizing agents, epoxy-urentane sizing agents, polyamide sizing agents, and olefin sizing agents. Among these, epoxy-based, polyamide-based, and urethane-based materials are preferable because of their good dispersibility with respect to the polycarbonate resin.
The amount of the surface treatment agent is preferably in the range of 0.5 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the nickel-coated carbon fiber (B2). .

  The ratio of the carbon fiber (B1) to the nickel-coated carbon fiber (B2) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, as a mass ratio of B1 / B2. More preferably, it is 3/7 to 7/3.

  The content of the carbon fiber (B) including the nickel-coated carbon fiber in the polycarbonate resin composition of the present invention, that is, the total amount of the carbon fiber (B1) and the nickel-coated carbon fiber (B2) is 100 parts by mass of the polycarbonate resin (A). It is 5-100 mass parts with respect to. If it is less than 5 parts by mass, the thermal conductivity and the electromagnetic wave shielding properties are insufficient. Conversely, if it exceeds 100 parts by mass, the impact resistance and fluidity are insufficient. Content of carbon fiber (B) becomes like this. Preferably it is 20 mass parts or more, More preferably, it is 25 mass parts or more, Preferably it is 80 mass parts or less, More preferably, it is 65 mass parts or less.

[Phosphorus flame retardant (C)]
The polycarbonate resin composition of the present invention contains 3 to 30 parts by mass of the phosphorus-based flame retardant (C) with respect to 100 parts by mass of the polycarbonate resin (A). Thus, by containing a phosphorus flame retardant (C), the flame retardancy and fluidity of the polycarbonate resin composition of the present invention can be sufficiently improved. The strength can be kept good.

  The phosphorus-based flame retardant (C) is a compound containing phosphorus in the molecule and may be a low molecule, an oligomer, or a polymer. From the viewpoint of thermal stability, for example, the following The phosphate compound represented by the general formula (1) and the phosphazene compounds represented by the following general formulas (2) and (3) are particularly preferable.

-Phosphate ester compound The phosphate ester compound represented by the general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of condensed phosphate esters having different k, k is the average value of the mixture. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

Specific examples of the phosphate ester compound represented by the general formula (1) include
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

  The acid value of the phosphoric acid ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less, particularly preferably Is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero.

  As the phosphate ester compound used in the present invention, in addition to the above-mentioned compounds, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3 -Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphoric acid Naturally, polyester resins, polycarbonate resins or epoxy resins containing an ester moiety are also included.

Phosphazene compound Examples of the phosphazene compound represented by the general formulas (2) and (3) include phenoxyphosphazene and (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p- Cyclic, such as tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene), (poly) xylyloxyphosphazene and / or or linear _{C 1-6} alkyl _{C 6-20} aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- Toriruokishiho Phazen, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxyxyloxyphosphazene And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene.
Of these, cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 Aryloxyphosphazenes (eg, cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.).

In the cyclic phosphazene compound represented by the general formula (2), R ⁵ and R ⁶ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ⁵ and R ⁶ are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in general formula (2), although t represents the integer of 3-25, the compound whose t is an integer of 3-8 is preferable especially, and the mixture of the compound from which t differs may be sufficient. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

In General Formula (3), R ⁷ and R ⁸ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, and the like, and a chain phenoxyphosphazene in which R ⁷ and R ⁸ are phenyl groups is particularly preferable.
Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

Also, R ⁹ is represented by -N = P (OR ⁷ ) ₃ groups, -N = P (OR ⁸ ) ₃ groups, -N = P (O) OR ⁷ groups, and -N = P (O) OR ⁸ groups. At least one selected is shown, and R ¹⁰ is -P (OR ⁷ ) ₄ group, -P (OR ⁸ ) ₄ group, -P (O) (OR ⁷ ) ₂ group, -P (O) (OR ⁸ ) At least one selected from _two groups.

  Moreover, in general formula (3), u shows the integer of 3-10,000, Preferably it is 3-1,000, More preferably, it is 3-100, More preferably, it is 3-25.

Further, the phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
As such a crosslinked phosphazene compound, a crosslinked structure represented by the following general formula (4), for example, a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, bisphenol S residue), 2,2- ( 4,4′-diphenylene) isopropylidene group-crosslinked structure, 4,4′-oxydiphenylene group-crosslinked structure, 4,4′-thiodiphenylene group-crosslinked structure, etc. And compounds having a crosslinked structure of 4,4′-diphenylene group.

[In Formula (4), X ² is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and v is 0 or 1. ]

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ⁵ and R ⁶ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (4). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (3) with a crosslinking group represented by the general formula (4) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (2) and the cyclic phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  As described above, the content of the phosphorus-based flame retardant (C) is 3 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), preferably 3.5 parts by mass or more, more preferably 4 parts. It is not less than 25 parts by mass, preferably not more than 20 parts by mass, more preferably not more than 15 parts by mass.

[Fluoropolymer (D)]
The polycarbonate resin composition of the present invention contains a fluoropolymer (D) as an anti-dripping agent.
Examples of the fluoropolymer (D) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril-forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J”, “Teflon (registered trademark) 6C” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Daikin Industries, Ltd. “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500H”, and the like are available. Furthermore, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon D” manufactured by Daikin Industries, Ltd. -1 "and the like.

Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like.
In addition, 1 type may contain fluoropolymer (D) and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer (D) is 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). More preferably, it is 0.1 parts by mass or more, and 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less. When the content of the fluoropolymer (D) is less than the lower limit of the above range, the effect of improving the flame retardancy by the fluoropolymer becomes insufficient, and when the content of the fluoropolymer exceeds the upper limit of the above range, the polycarbonate Deterioration in appearance and mechanical strength of the molded product obtained by molding the resin composition are likely to occur.

[Elastomer]
The polycarbonate resin composition of the present invention preferably contains an elastomer. The content of the elastomer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), and the upper limit thereof is preferably 10 parts by mass or less. . When the elastomer content is less than the lower limit value, the impact resistance improvement effect by the elastomer tends to be insufficient, and when the elastomer content exceeds the upper limit value, flame retardancy, heat resistance, reduced impact resistance, molded product The appearance defect is likely to occur.

The elastomer is preferably a thermoplastic elastomer or a core / shell type graft copolymer type elastomer.
A thermoplastic elastomer is a general term for polymer substances having a property of being melt-mixable with a thermoplastic resin, which is a solid having rubber-like elasticity at room temperature, but whose viscosity decreases when heated. The type of the thermoplastic elastomer is not particularly limited, and examples thereof include olefin, styrene, polyester, polyamide, and urethane.
As a core / shell type graft copolymer type, a polybutadiene-containing rubber or a polyorganosiloxane rubber is used as a core layer, and a shell layer formed by copolymerizing (meth) acrylic acid ester around the core layer. A core / shell type graft copolymer is particularly preferred.

[Release agent]
The polycarbonate resin composition of the present invention preferably contains a release agent. Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oils, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized. The number average molecular weight is preferably 5,000 or less. The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, paraffin wax and polyethylene wax are more preferable, and polyethylene wax is particularly preferable.

In addition, 1 type may contain the mold release agent and 2 or more types may contain it by arbitrary combinations and a ratio.
The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). It is below mass parts. When the content of the release agent is less than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[Other ingredients]
The polycarbonate resin composition of the present invention may contain other components other than the above, if necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives other than those described above. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) ), Styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin); polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; Resin; Polysulfone resin etc. are mentioned.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.
When other resin is contained, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, in total 100 parts by mass of the polycarbonate resin (A) and other resins, and 20 parts by mass. More preferably, it is as follows.

Resin additives Examples of resin additives include heat stabilizers, antioxidants, glass fibers, UV absorbers, dyes and pigments (including carbon black), antistatic agents, antifogging agents, lubricants, antiblocking agents, Examples thereof include a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[Production Method of Polycarbonate Resin Composition]
There is no limitation on the production method of the polycarbonate resin composition of the present invention, and a wide variety of production methods of known polycarbonate resin compositions can be adopted. Polycarbonate resin (A), carbon fiber containing nickel-coated carbon fiber (B), phosphorus-based difficulty The flame retardant (C) and the fluoropolymer (D), and other components to be blended as necessary, are mixed in advance using various mixers such as a tumbler and a Henschel mixer, then, a Banbury mixer, a roll, a Brabender, Examples thereof include a melt kneading method using a mixer such as a single screw kneading extruder, a twin screw kneading extruder, or a kneader. When using a biaxial kneading extruder, the carbon fiber (B1) and the nickel-coated carbon fiber (B2) are preferably side-fed.
The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

[Molding]
The pellets obtained by pelletizing the above-described polycarbonate resin composition are molded into various molded products by various molding methods. Further, the resin melt-kneaded by an extruder can be directly molded into a molded product without going through the pellets.
The shape of the molded product is not particularly limited and can be appropriately selected according to the use and purpose of the molded product. For example, the shape of the plate, plate, rod, sheet, film, cylindrical, annular, Examples include a circular shape, an elliptical shape, a polygonal shape, an irregular shape, a hollow shape, a frame shape, a box shape, and a panel shape.

  The method for molding the molded body is not particularly limited, and a conventionally known molding method can be employed.For example, an injection molding method, an injection compression molding method, an extrusion molding method, a profile extrusion method, a transfer molding method, a hollow molding method, Gas assisted hollow molding method, blow molding method, extrusion blow molding, IMC (in-mold coating molding) molding method, rotational molding method, multilayer molding method, two-color molding method, insert molding method, sandwich molding method, foam molding method And a pressure molding method.

  The polycarbonate resin composition of the present invention is a highly heat conductive and electromagnetic shielding resin material having high thermal conductivity and high electromagnetic shielding properties, and excellent in flame retardancy and strength. It can be suitably used in the fields of electrical equipment, OA equipment, transportation equipment such as automobiles, and various mechanical equipment. In particular, a molded product obtained by molding this is particularly suitable for a housing, a housing, etc. of a personal computer, a digital camera or various portable terminals.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
Each raw material component used in the following Examples and Comparative Examples is as shown in Table 1 below.

(Examples 1-12, Comparative Examples 1-2)
Each component described in Table 1 above was blended in the proportions shown in Table 3 below (all expressed in parts by mass) and uniformly mixed with a tumbler mixer, and then a twin screw extruder (TEX30HSST manufactured by Nippon Steel Works). ), The cylinder temperature is 280 ° C., the screw rotation speed is 200 rpm, the discharge amount is 20 kg / hr, and the feed is fed to the extruder from the barrel upstream of the extruder, and the carbon fiber and the nickel-coated carbon fiber are side-fed and melt-kneaded. To obtain pellets of the polycarbonate resin composition.

[Molding of ISO multipurpose specimen]
After drying the above pellets at 100 ° C. for 5 hours, using an injection molding machine (“J55-60H” manufactured by Nippon Steel), cylinder set temperature 280-300 ° C., mold temperature 100 ° C., injection time 2 seconds, molding cycle 40 Injection molding was performed under the conditions of seconds, and an ISO multipurpose test piece (4 mm thick) was injection molded.

[Evaluation of tensile properties]
Using the above ISO test piece (4 mm), in accordance with ISO standard 527-1 and ISO 527-2, tensile elastic modulus (unit: MPa), tensile strength (unit: MPa), fracture point nominal strain (unit:%) Was measured.

[Evaluation of bending properties]
Based on ISO178, the bending modulus (unit: MPa) and bending stress (unit: MPa) were measured at 23 ° C. using the ISO test piece (4 mm).

[Evaluation of heat resistance: DTUL (deflection temperature under load, unit: ° C)]
Using the ISO multipurpose test piece obtained above, the measurement was performed under the condition (Method A) under a load of 1.80 MPa according to ISO 75-1 & 2. In the table, “DTUL” is used.

[Measurement of thermal conductivity (unit: W / m · K)]
The ISO multipurpose test piece (4 mm) obtained above was cut into a slice of 0.15 to 0.5 mm thickness, and this was used as a sample. Temperature phase thermal analyzer “ai-Phase Mobile1” manufactured by I-Phase Co., Ltd. Was used to measure the MD direction (resin flow direction during molding) and the thickness direction.

[Evaluation of flammability: UL94 test]
The pellets are dried at 100 ° C. for 5 hours, and then injection molded by an injection molding machine (“J55-60H” manufactured by Nippon Steel) under conditions of a cylinder set temperature of 340 ° C., a mold temperature of 120 ° C., and a molding cycle of 30 seconds. Two test pieces for UL test having a length of 125 mm and a width of 13 mm and a thickness of 1.5 mm were molded.
The obtained specimens were conditioned for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity, and UL94 test (combustion of plastic materials for equipment parts) was established by US Underwriters Laboratories (UL). Test). UL94V is a method for evaluating the flammability from the afterflame time and the drip property after the flame of the burner is indirectly fired for 10 seconds on a test piece of a predetermined size held vertically. V-0, V-1 And in order to have V-2 flammability, it is necessary to satisfy the criteria shown in Table 2 below.

Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.
The above evaluation results are shown in Table 3 below.

[Evaluation of electric field shielding performance and magnetic field shielding performance]
Next, the pellets of the obtained resin composition were dried at 100 ° C. for 5 hours, and then the cylinder set temperature was 300 ° C., the mold temperature was 100 ° C., and the molding cycle was performed with an injection molding machine (“J180” manufactured by Nippon Steel) Injection molding was performed under a condition of 45 seconds to obtain a flat plate type test piece of 150 mm × 150 mm × 2 mm.
About the obtained test piece, the electric field shielding performance (unit: dB) and magnetic field shielding performance (unit: dB) in 200-1000 MHz were measured with the electromagnetic shielding property measuring apparatus based on KEC method.
The results are shown in Table 4 below.

  The polycarbonate resin composition of the present invention has high thermal conductivity and high electromagnetic shielding properties, and is excellent in flame retardancy and strength. Therefore, various electronic electrical equipment, OA equipment, transportation equipment such as automobiles, various machines, etc. It can be suitably used in the field of equipment and the like, and is particularly suitable for housings, housings and the like of personal computers, digital cameras or various portable terminals, and has very high industrial applicability.

Claims (3)

5 to 100 parts by mass of carbon fiber (B) containing nickel-coated carbon fiber, 3 to 30 parts by mass of phosphorus flame retardant (C), and 0 to fluoropolymer (D) with respect to 100 parts by mass of polycarbonate resin (A) 0.001 to 5 parts by mass ,
The carbon fiber (B) is a mixture of pitch-based carbon fiber (B1) and nickel-coated PAN-based carbon fiber (B2), and the mass ratio of content (B1 / B2) is 3/7 to 7/3. A polycarbonate resin composition characterized by that.   The polycarbonate resin composition according to claim 1, wherein the phosphorus-based flame retardant (C) is a phosphate ester compound or a phosphazene compound. Claim 1 or 2 molded article obtained by molding the polycarbonate resin composition according to.